CN1073579C - Polyurethane polymer or oligomer having carbamate groups, method for its preparation, and coating composition - Google Patents

Polyurethane polymer or oligomer having carbamate groups, method for its preparation, and coating composition Download PDF

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CN1073579C
CN1073579C CN95120881A CN95120881A CN1073579C CN 1073579 C CN1073579 C CN 1073579C CN 95120881 A CN95120881 A CN 95120881A CN 95120881 A CN95120881 A CN 95120881A CN 1073579 C CN1073579 C CN 1073579C
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urethane
cyclic carbonate
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CN1139123A (en
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G·G·麦诺夫希克
W·H·奥尔伯姆
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C09D201/025—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
    • C08G18/3823—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing -N-C=O groups
    • C08G18/3831—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing -N-C=O groups containing urethane groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
    • C08G18/807—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with nitrogen containing compounds
    • C08G18/8077—Oximes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular

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  • Wood Science & Technology (AREA)
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  • Paints Or Removers (AREA)

Abstract

Polyurethane polymers having pendant carbamate groups are disclosed. The polymers are prepared by: (a) reacting a mixture comprising a polyol having at least one pendant carbamate group and a polyisocyanate to form a polyurethane having pendant carbamate groups, and (b) optionally, capping the polyurethane from (b) with an active hydrogen-containing capping agent.

Description

The urethane and preparation method thereof and the coating composition that have carbamate groups
The present invention relates to superpolymer, specifically relate to contain the curable coating composition of superpolymer.
The superpolymer and the oligopolymer that have carbamate-functional have been applied in the various curable compositions.For example, United States Patent (USP) U.S.5,356,669 and WO94/10211 narrated the vinylformic acid superpolymer that has carbamate-functional.These superpolymer can perhaps make by hydroxyl functional group's vinylformic acid and alkyl carbamate are carried out the carboxylamine transesterification reaction by carrying out addition polymerization to the Acrylic Acid Monomer of band carbamate-functional.The polyester of also having narrated in JP51/4124 by hydroxyl functional group carries out the method that the carboxylamine transesterification reaction prepares the polyester of being with carbamate-functional.
Urethane resin also is widely used in the curable compositions such as coating composition.These resins provide many useful performances, such as favorable durability, stablize group and obtain dispersiveness good in water solution system, shock-resistance, good adhesivity and other physical properties by mixing suitable ionic or non-ionic type, such as stress relieving performance etc.The field that relevant urethane resin is used for curable compositions is to mix the functional group of q.s to reach desired curing performance toward resin.In curable compositions, hydroxyl is normally used functional group, but the urethane resin that has pendant hydroxyl group is difficult to preparation, because any pendant hydroxyl group all will be consumed with isocyanate reaction in the process that forms urethane.The hydroxyl-functional base is normally by incorporating the agent of polyvalent alcohol end-block on the urethane resin into such as TriMethylolPropane(TMP), thereby produces end group OH base, rather than side OH base.This resinoid can only provide limited degree of crosslinking when solidifying.By the urethane that uses the band fork chain degree of crosslinking is had to a certain degree increases, and this urethane can make by trifunctional base or higher functional group's polyvalent alcohol is incorporated in the polyurethane reactive mixture.But because pectisation, the degree of band fork chain usually is restricted.Low crosslinking degree usually must compensate by the resin with higher molecular weight, and the latter is more similar to thermoplastic compounds, and unlike thermoset composition.
United States Patent (USP) U.S.5 has described the urethane of band carbamate-functional in 373,069.Described in this reference by various methodologies, such as the method for coming the urethane of blocked isocyanate end group with hydroxyalkyl carbamate, prepared the urethane that has the carboxylamine ester terminal.This reference also discloses the method for preparing the urethane that has side carbamateyl, and it is the urethane that at first has side carboxyl by the known technology preparation, then carboxyl and hydroxyalkyl carbamate is carried out transesterification reaction.The related route of synthesis of this method may be difficult.Also have, it causes consuming the carboxyl on the polyurethane(s), thereby influences the stability of resin in the aqueous solution.
Therefore, the purpose of this invention is to provide a kind of new preparation and have the urethane superpolymer of side carbamateyl or the method for oligopolymer.It also provides a kind of and had both had side carbamateyl, also has a urethane resin of side carboxyl.
According to the present invention, a kind of method for preparing urethane superpolymer or oligopolymer is provided, it comprises:
(a) make the polyvalent alcohol that contains at least one side carbamateyl and the mixture reaction of polyisocyanates, have the urethane of side carbamateyl with formation;
(b) alternatively, the urethane that is obtained by (b) is sealed end group with the end-capping reagent that contains reactive hydrogen.
Another specific embodiments of the present invention provides a kind of urethane superpolymer or oligopolymer that has carboxyl and carbamate groups simultaneously.
In another specific embodiments of the present invention, curable coating composition also is provided, it contain above-mentioned band carbamate-functional urethane and can with the solidifying agent of carbamate radical reaction.
The polyvalent alcohol that has at least one carbamate groups thereon can be prepared by several different methods.A kind of method is that the compound and ammonia, ammonium hydroxide or the primary amine that have a plurality of cyclic carbonate group are reacted to open the ring of cyclic carbonate group.This ring-opening reaction can be converted into a hydroxyl and a side carbamateyl to the ring of each cyclic carbonate.
The compound that has a plurality of cyclic carbonate group can prepare with several methods.A kind of technology is that polyisocyanates or multi-anhydride and hydroxyalkyl cyclic carbonate are reacted.The hydroxyalkyl cyclic carbonate can be prepared by a number of procedures.There are some hydroxyalkyl cyclic carbonates can buy from the market such as 3-hydroxypropyl carbonic ether (being glycerol carbonate).Cyclic carbonate compound can synthesize with in some different methods any.A kind of method is the compound and the CO that contain epoxy group(ing) 2React, preferably under the condition of pressurizeing and having catalyzer to exist, react.Useful catalysts comprises any compound that can activate oxirane ring, such as by the double salt of quaternary ammonium salt (for example 4 bromide), tin and/or the phosphorus of tertiary amine system ((CH for example 3) 3SnI, (CH 3) 4PI).Epoxide also can react with β-butyrolactone under the condition that this class catalyzer exists.Another method be glycol such as glycerine at (normally under refluxad) under at least 80 ℃ the temperature, under the condition that a kind of catalyzer (for example salt of wormwood) exists, react, to form the hydroxy alkyl carbonate ester with diethyl carbonate.In addition, what have following structure contains 1, functional group's compound of 2-glycol ketal: Can under at least 60 ℃ temperature, when preferably having micro-acid to exist, carry out ring-opening reaction and form 1 with water, the 2-glycol, it further forms the cyclic carbonic ether with the diethyl carbonate reaction again.
The cyclic carbonic ether has 5-6 unit ring usually, and is such as known in the profession.Preferably use pentacyclic because they are easily synthetic and be easier to buy from market.The preferred hydroxyalkyl cyclic carbonate that uses in the reality can be represented with following formula:
Figure C9512088100072
Wherein R is the hydroxyalkyl that contains 1-18 carbon atom, preferably contains 1-6 carbon atom, more preferably contains 1-3 carbon atom; The n value is 1 or 2.Can also be replaced by amino or the unsaturated group of one or more substituting groups on it such as sealing.More preferred R is-C mH 2mOH, hydroxyl wherein can be one-level or secondary, and the m value is 1-8; Preferred R is-(CH 2) P-OH, hydroxyl wherein is an one-level, the P value is 1 to 2.
Can be any polyisocyanates basically with the organic multiple isocyanate of hydroxyalkyl cyclic carbonate reaction, but vulcabond preferably, the vulcabond of hydro carbons or replace the vulcabond of hydro carbons for example.Many these class organic diisocyanates are known in this specialty, comprise PPDI, biphenyl-4,4 '-vulcabond, the methyl vulcabond, 3,3 '-dimethyl-4,4 '-biphenyl diisocyanate, 1, the 4-tetramethylene diisocyanate, 1, the 6-hexamethylene diisocyanate, 2,2,4-trimethyl cyclohexane-1, the 6-vulcabond, methylene-bis (phenyl isocyanate), 1, the 5-naphthalene diisocyanate, two (fumaric acid isocyanato ethyl), isophorone diisocyanate (IPDI), tetramethylxylene diisocyanate and methylene radical-two-(4-cyclohexyl isocyanate).Here also can use isocyanate-terminated glycol, such as ethylene glycol or 1, the affixture of 4-butyleneglycol etc.These compounds can be by more than one mole vulcabond, as top said those, react with one mole glycol and form a kind of long chain vulcabond.In addition, glycol also can add together with vulcabond.
Though vulcabond is preferred, also can use other multifunctional isocyanate.Example has 1,2,4-benzene triisocyanate and polymethylene polyphenyl isocyanate.
Reaction between polyisocyanates and the hydroxyalkyl cyclic carbonate can be carried out under the condition that the known pure and mild isocyanic ester of this specialty reacts.
Can comprise in this specialty any in known this compounds with the multi-anhydride of hydroxyalkyl cyclic carbonate reaction, for example hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, maleic anhydride, L-glutamic acid acid anhydride, hexanaphthene-1,2,4,5-bisgallic acid acid anhydride.The condition that this reaction is carried out is generally temperature at least at 80 ℃, and preferably 98-120 ℃, and have the tin metal catalyzer to exist.
The compound that has a plurality of cyclic carbonate group also can be easily by making polyepoxide and carbon dioxide reaction, epoxy group(ing) is converted into cyclic carbonate group makes.Polyepoxide is well-known in this specialty.Useful polyepoxide comprise by with epichlorohydrin reaction by epoxidised TriMethylolPropane(TMP) derivative and epoxy phenolics.Also can use oligomeric or high poly-polyepoxide, such as the vinylformic acid superpolymer or the oligopolymer of the polyglycidyl ether that contains glycidyl methacrylate or epoxidation end group.Also can use other polyepoxide, for example epoxidization phenolic resin.As other polyepoxide, epoxidization phenolic resin also can form cyclic carbonate compound with carbon dioxide reaction.
Have the compound that two functional groups carry out reactive urethane though the urethane of line style will mainly be based on, the cyclic carbonate that is higher than 3 functional groups also can be expected provides the urethane of band fork chain.For example, can produce four functional groups' alcohol with polyvalent alcohol such as TriMethylolPropane(TMP) adduction in vulcabond such as the isocyanate group in the isophorone diisocyanate molecule, it can produce the polynary epoxide of four-functional group with epoxyhalopropane initial ring oxidizing reaction, and then just can form it and carbon dioxide reaction the cyclic carbonate of four-functional group.Other has the more polynary epoxide of high functionality, four (4-glycidyl oxygen base phenyl) ethane for example, also can with CO 2React and formation polybasic cyclic carbonate.
The compound that has a plurality of cyclic carbonate group can react with ammonia, ammonium hydroxide or primary amine.(for example 0-60 ℃, in water, methyl alcohol or other known solvent) finished in this reaction under mild reaction conditions.Produce the primary amine carbamate with ammonia or ammonium hydroxide reaction, and be preferred.Produce secondary (N-replaces) carbamate with primary amine reaction.The ring-opening reaction of ammonia, ammonium hydroxide or primary amine and cyclic carbonate group produces above-mentioned carbamate groups and one-level or secondary hydroxyl, and the latter will participate in forming the reaction of urethane in next step of the present invention.So this reaction product band side carbamateyl and terminal hydroxy group.
Another kind of preparation has the technology of the polyvalent alcohol of a side carbamateyl at least, is that hydroxyalkyl cyclic carbonate and ammonia, ammonium hydroxide or primary amine are reacted.This reaction can be finished according to the method that the above-mentioned compound that has a plurality of cyclic carbonate group carries out ring-opening reaction.The compound that obtains has two hydroxyls and a side carbamateyl.
Side carbamateyl in polyurethane molecular of the present invention can be one-level or secondary.The carbamate groups of one-level can be represented with following formula: And the carbamate groups of secondary can be represented with following formula:
Figure C9512088100102
Wherein R be contain 1-8 carbon atom, preferably 1-4 carbon atom, more preferably 1 carbon atom replacement or come substituted alkyl, or cycloaliphatic radical.Should be appreciated that term alkyl and cycloalkyl comprise the alkyl and the cycloalkyl of replacement, such as the alkyl or cycloalkyl of halogen replacement, or the alkyl of unsaturated group replacement.But should avoid the substituting group that uses those performances to have disadvantageous effect to the solidified material.By using ammonia or ammonium hydroxide as the ring-opening reaction thing, what form in the ring-opening reaction of above-mentioned cyclic carbonate is the primary amine carbamate.
In step of the present invention (b), a kind of mixture that contains the reaction product that obtained by step (a) and polyisocyanates reacts and forms urethane.Also contain the component that other is used to prepare urethane in this mixture, such as other monomer, polyvalent alcohol, aliph polyols is oligomeric or high poly-polyvalent alcohol, other polyisocyanates, polyisocyanates give polymers, polyamine, amino alcohol, three isocyanide acid alcohols or the like.According to required result, said components can be reacted in same reactor, also can react in order.Reacting the structure of the resin of generation in order can control.The reaction product of step (a) and other above-mentioned compound that has active hydrogen group can be used as chainextender, if they have more than an active hydrogen group, then constitute the main chain of urethane by the reaction of active hydrogen group and isocyanate groups.For the polyfunctional compound that only contains an active hydrogen group, then the result is an end stopping of chain.Other chainextender that has at least two active hydrogen groups can be added into, so that increase the chemical property of chain length or change urethane resin.
Polyurethane reaction carries out under this professional well-known condition, typically below 100 ℃, in a kind of aprotic solvent (for example aromatic hydrocarbons, ester class, ketone), carries out under the condition that tin catalyst exists.The number-average molecular weight of the urethane resin that obtains is between 1000 to 40,000.
Generally, should use excessive polyisocyanates, to make a kind of intermediate urethane that has the free isocyanate groups endways.The free isocyanate groups can seal end group with the known end-block agent that is used for isocyanic ester then.
The isocyanic ester that is used for step of the present invention (b) can be the central any isocyanic ester of compound that above-mentioned preparation has a plurality of cyclic carbonate groups.Can be used alone, also can be used in combination several.
A kind of aliphatic diisocyanate of often preferred use can provide improved weathering resistance for the coating that obtains because have been found that them.Specific examples comprises 1,6-hexamethylene diisocyanate, 1,4-fourth vulcabond, methylene radical-two-(4-cyclohexyl isocyanate) and isophorone diisocyanate.Also can use the mixture of these vulcabond.
The reaction product of polyisocyanates, step (a) and any ratio that other contains the compound of reactive hydrogen can be selected like this, and a kind of reactive hydrogen terminated urethane resin or a kind of isocyanate-terminated intermediate urethane resin can be provided.This can accomplish by using excessive active hydrogen compounds or the polyisocyanates of stoichiometry.
If wishing has well water-soluble, then importantly to incorporate the group of water-stable in the molecule of urethane into.The acidic-group that this class group can be an anionic property (for example carboxyl), or the group of nonionic (for example polyethers).For example, in the existing in of acidic-group and the time composition is become can be by water-reducible.
Be used in urethane resin of the present invention, providing the acids of free acidic group easily to obtain.They contain an active hydrogen group and at least one carboxylic-acid functional base at least.Active hydrogen group can be mercaptan, hydroxyl or amino.Primary amine is considered to have an active hydrogen group; The example of this compounds comprises hydroxycarboxylic acid, amino acid, mercaptan acid, amino mercapto acid, alkanol amino acid and hydroxyl mercaptan acid.
Preferably use the compound that contains at least two hydroxyls and at least one carboxyl, they can be prepared by the aldehydes that has two hydrogen atoms on alpha-position at least.Such aldehydes forms 2 with bimolecular formaldehyde reaction under the condition that alkaline catalysts exists, 2-dihydroxymethyl aldehyde is then the aldehyde that obtains mildly oxidising one-tenth acid in accordance with known methods.The acids of Shi Yonging can be represented with the following formula I simply in the present invention: Wherein R represents methylol, hydrogen or 20 carbon atoms are arranged at most, preferably the alkyl of 8 carbon atoms arranged at most.
The concrete example of this class acid of Shi Yonging comprises 2 in the present invention, 2-two (methylol) acetate, 2,2,2-three (methylol) acetate, 2,2-two (methylol) propionic acid, 2,2-two (methylol) butyric acid, 2,2-two (methylol) valeric acids etc., wherein preferred acid is 2,2-two (methylol) propionic acid.
Give superpolymer is known in this specialty with water miscible polyethers with can be used to nonionic, and is for example narrating among the United States Patent (USP) U.S.4794147, and its disclosure is incorporated herein by reference.Useful polyether compound is simple function group or bifunctional polyethers preferably, preferably the polyethers of simple function group.Functional group on pfpe molecule can be alcohol radical, thiol group, amine or these functional groups' combination.The polyethers of monofunctional can be formed by the monohydroxy-alcohol initiated polymerization by oxyethane, propylene oxide and their mixture.The polyether compound that contains 100% ethylene oxide unit is particularly preferred.When polyether group is used as the water-stable group, calculate by the weight of final urethane resin, its content is preferably between 5-25%, and molecular weight is 1, and 000-3 is between 000.
By with containing at least two active hydrogen groups but the mixture that does not contain a kind of compound of hydroxy acid group or several these compounds increases the chain length of urethane, can obtain the more urethane resin of long-chain.These compounds have, for example glycols, dithiols, two amines or have hydroxyl, sulfydryl and amino compound, for example alkanol amine, aminoalkyl group thio-alcohol and hydroxyalkyl thio-alcohol and other this compounds of combination.For the purpose of this respect of the present invention, the firsts and seconds amido all is considered to have the group of a reactive hydrogen.The alkanol amine, for example thanomin or diethanolamine are preferred chainextenders, most preferably use glycols.The example that is used as the preferred glycols of polyurethane chain extender comprises 1,6-hexylene glycol, hydroxymethyl-cyclohexane and 1,4-butyleneglycol.Also can be used as chainextender though contain the polyol of at least three hydroxyls, use these compounds can produce the urethane resin of band fork chain.Be purpose of the present invention, preferably reduce the quantity of fork chain in the urethane resin as far as possible, if therefore use polyol, they preferably only limit to occupy a small amount of deal in the mixture that urethane produces.The polyol of these higher functionalization for example comprises TriMethylolPropane(TMP), trimethylolethane, tetramethylolmethane and other compound.
This urethane resin can come chain extension by any way with the multiple functional radical compound that has at least two active hydrogen groups.For example, can be added to these compounds in the polyvalent alcohol and the formed mixture of polyfunctional compound of polymeric polyisocyanate, amido-containing acid ester, also can react in addition, be present in two free isocyanate group of intermediate urethane resin end with bonding an intermediate steps.
The intermediate urethane resin of Chan Shenging can have free isocyanate group end group like this.For this reason, can use excessive polyisocyanates component.Certainly, the molar weight of other component also should be adjusted according to the characteristic of required intermediate and final urethane resin.Press the weight of reaction mixture and calculate, it is about 45% that the polyvalent alcohol component should be no more than, and the weight calculating of press reactant in the mixture, and preferably polyvalent alcohol component content is about 30% to about 40%.
In preferred specific embodiments of the present invention, be to use a kind of simple function group or multi-functional alcohol to come (sealing free isocyanate group) (mensuration of the isocyanate groups concentration by viscosity and existence is differentiated the degree that reaction is carried out) of termination reaction in required step.Wish especially for this purpose to use amino alcohol, such as thanomin, diethanolamine etc., because amino preferentially reacts with the isocyanate groups that exists.Multi-functional alcohol also can be used by this way such as ethylene glycol, TriMethylolPropane(TMP) and hydroxyl terminated polyester etc.Do not have hydroxy functional group if resin only has carbamate-functional, the then this intermediate urethane resin alcohol or the amine (for example propyl carbinol) of handy simple function group seals end group.
The weight that the content of polyisocyanates is pressed reactant in the mixture in mixture is calculated preferably between about 20% to 30%, but also will depend on known other factors in the molecular weight of the acid number (if using group of the water-stable of anionic property) of the amount that whether has other polyvalent alcohol and existence, required final urethane resin, required final urethane resin and this specialty and change.The consumption of polyisocyanates also will depend on and whether need a terminal and have the intermediate urethane of free isocyanate group or hydroxyl and change.For example, under the occasion of the urethane end group that has free isocyanate groups that preferably need seal, just should use excessive polyisocyanates with a kind of alcohol.And, then to use substoichiometric polyisocyanates in the occasion that the intermediate urethane resin seals end group like this.
When urethane uses tart water-stable group, the consumption that has a polyfunctional group component of at least one active hydrogen group and at least one water-stable group will depend on the acid number of required final urethane resin and change.The acid number that final urethane resin should have is at least about 10, according to reaction mixture (polyisocyanates, polyvalent alcohol, polyfunctional compound, other alternative chainextender of producing urethane, for example have two active hydrogen groups but not with the compound of carboxyl) in the weight of reactant calculate, the content of this polyfunctional group component should be between about 1% to about 25%.Acid number is preferably higher, because when acid number increases, the dispersiveness of urethane resin in water also greatly increases.Certainly, the upper limit of acid number will depend on the composition of final urethane and change, but generally speaking, and acid number is about 100 to be actual upper bounds of urethane of the present invention.
When being used for preparing urethane resin, calculate based on the weight of reactant, the content of chainextender (reaction product and other chainextender that comprise step (a)) changes between 2% to 25% greatly.The actual amount of using will depend on the degree of required chain extension and the molecular weight of required polyurethane molecular.
Synthetic contain the urethane resin of negatively charged ion ground after water-soluble after, a part of free hydroxy-acid group is with alkali neutralization and formation carboxylate group.Preferably used alkali is to contain amino compound.Tertiary amine is better than firsts and seconds amine, because firsts and seconds amine tends to react with aminoplast crosslinking agent.Comprise trialkylamine through preferred tertiary amine, for example Trimethylamine 99 and triethylamine.Trolamine also is preferred, but particularly preferably is dimethylethanolamine.
Urethane resin of the present invention can with other component be mixed with together can spray or electrostatic precipitation in metal or frosting, the coating composition on the car body for example.Generally, urethane resin prescription described herein is with solidifying agent, with together resin, water and/or organic solvent of pigment grind, comprises that the pigment of aluminium and/or mica particles and rheology control agent mix.Also can comprise other reagent, for example various fillers, tensio-active agent, softening agent, stablizer, wetting agent, dispersion agent, defoamer, adhesion promoter and little amount of catalyst.
As pointing out that the dispersion of urethane resin is to be used as primary or main automobile-used resin.Generally, the content of this primary or main automobile-used resin account for be present in the primer composition solid amount about 20 to 80% between.
In curable compositions of the present invention, curing is to realize by the reaction of the polyurethane component of amido-containing acid ester functional group and component (2), and component (2) is the compound that has many functional groups that can react with the side carbamateyl group on the urethane.This class active group is included in methylol or the methyl alkoxy on aminoplast crosslinking agent or other compound, such as phenol/formaldehyde adducts, siloxanes and anhydride group etc.The example of solidifying agent comprise melamino-formaldehyde resin (comprising monomeric or polymeric melamine resin and part or all of alkylating melamine resin), urea resin (for example the methylol ureas, as urea-formaldehyde resin, alkoxyl group ureas such as butylated urea formaldehyde resin), poly-anhydrides (for example poly-succinic acid anhydride) and polysiloxane-based (for example trimethoxy siloxane).Particularly preferably be aminoplast(ic) resin such as melamino-formaldehyde resin or urea-formaldehyde resin.
Alternative in practical application of the present invention is to use a kind of solvent in curable compositions.Though according to compositions for use of the present invention for example can be that the form of pressed powder or a kind of dispersion is used basically, usually wish also that composition can use with liquid basically form, this can accomplish by using solvent.This solvent should be the solvent of the urethane of band carbamate-functional, also is the solvent of solidifying agent.Generally, depend on the dissolubility property of component, this solvent can be any organic solvent and/or water.In a preferred specific embodiments, solvent is a kind of polar organic solvent.The solvent of comparative optimization is polar aliphatic solvent or polar aromatic solvent.Preferred solvent is the sulfone of the acid amides of ketone, ester, acetic ester, non-proton property, non-proton property or the amine of non-proton property.Useful examples of solvents comprises the mixture of methyl ethyl ketone, methyl iso-butyl ketone (MIBK), amyl acetate-n, ethylene glycol butyl ether acetate, propylene glycol monomethyl ether acetate, dimethylbenzene, N-Methyl pyrrolidone or arene.In another preferred specific embodiments, solvent is the mixture of water or water and a small amount of solubility promoter.
Comprise also in the curable compositions of practical application of the present invention that catalyzer is to quicken curing reaction.For example, when using aminoplast compounds, particularly during monomeric melamine compounds, can using a kind of strong acid catalyst to quicken curing reaction.This class catalyzer is well-known in this specialty, for example comprises tosic acid, dinonylnaphthalene disulfonic acid, Witco 1298 Soft Acid, acid phosphatase phenyl ester, butyl maleate, butyl phosphate and hydroxyl phosphate.Strong acid catalyst for example Chang Keyong amine is protected.Operable other catalyzer comprises Lewis acid, zinc salt and pink salt in composition of the present invention.
In a preferred specific embodiments of the present invention, the solvent that is present in the curable compositions is that about 0.01 weight % is to about 99 weight %, preferably about 10 weight % are to about 60 weight %, and more preferably about 30 weight % are to about 50 weight %.
Coating composition can be coated on the object with any technology in the more well-known technology of this specialty.These technology for example comprise spraying coating, dip-coating, cylinder coating, curtain coating etc.For the car body panelling, preferably with spraying.
The reagent of any other use, for example tensio-active agent, filler, stablizer, wetting agent, dispersion agent, adhesion promoter, ultraviolet absorbers, HALS etc. can incorporate in the coating composition.Though these reagent are well-known, must control their consumption, in order to avoid coating property is brought adverse influence in prior art.
Curable compositions of the present invention preferably uses with high glossiness coating and/or as the Clear paint in the compound color-plus-clear coating.Here used high glossiness coating is meant that have 20 ° of gloss (ASTM D523-89 standard) or DOI value (ASTM E430-91 standard) is at least 80 coating.Curable compositions of the present invention also can be used as the priming paint in the compound color-plus-clear coating.
When coating composition of the present invention be used as high glossiness use the coating of pigment dyeing the time, used pigment can be any organic or inorganic compound or painted material, weighting agent, metal or other inorganic sheet material such as mica or aluminum slice, and other those in this specialty, be called as the material of pigment.The common consumption of pigment is 1% to 100% (be P: the ratio of B is 0.1 to 1) based on the total solid weight of component A and B in composition.
When coating composition of the present invention was used as Clear paint in the compound color-plus-clear coating, what chromatic primer composition can be with in the middle of more well-known types in this specialty was any, and need not here to illustrate in detail.The known superpolymer that is used as primer composition in this specialty comprises polyacrylic, polyethylene kind, polyurethanes, polycarbonate-based, polyester, Synolac class and polysiloxane-based.Preferred superpolymer comprises poly-propionic acid ester and polyurethanes.In a preferred specific embodiments of the present invention, basic unit's coating composition also uses the vinylformic acid superpolymer that has carbamate-functional.Basic unit's coating superpolymer can be thermoplastic, but preferably crosslinkable, and contains the crosslinkable functionality of one or more types.This class functional group for example comprises hydroxyl, isocyanate group, amino, epoxy group(ing), acrylate-based, vinyl, silylation and acetoacetate groups.These groups can be sheltered or protect in such a way, promptly when they are in required condition of cure, following time of condition of elevated temperature normally, can remove and shelter and can participate in crosslinking reaction.Useful crosslinkable functional group comprises hydroxyl, epoxy group(ing), carboxylic acid, acid anhydrides, silane and acetoacetate groups.Preferred crosslinkable functional group comprises hydroxyl-functional base and amino-functional base.
Basic unit's coating superpolymer can be that itself is crosslinkable, and also can be needs linking agent ability other, that can react with the functional group of this superpolymer crosslinked.When superpolymer contained the hydroxyl-functional base, linking agent for example can be isocyanic ester (comprising isocyanuric acid ester) and carboxylic acid or anhydride functional group's linking agent of aminoplast(ic) resin, isocyanic ester and protection.
Here Xu Shu coating composition preferably be placed in can the condition of solidified coating under.Though can use various curings, method preferably is heating and curing.Generally, being heating and curing is by applied object being exposed to mainly by the realization of getting off of the temperature of the rising that radiant heat source provided.Solidification value will depend on concrete blocking group used in the linking agent and change.But they generally are in 93 ℃ to 177 ℃ scope.Even compound of the present invention under lower solidification value also be respond active.For example, in a preferred specific embodiments, for the acid catalysis system of having protected, preferred solidification value is between 115 ℃ to 150 ℃, and preferred temperature is between 115 ℃ to 138 ℃.And for the acid catalysis system of protecting, solidification value is preferably between 82 ℃ to 99 ℃.To depend on the thickness of used concrete component and physical parameter such as coating set time and change, but scope was at 15 to 60 minutes for the acid catalysis system of having protected typical set time, preferably 15-25 minute; And for unprotected acid catalysis system, then set time, scope was 10-20 minute.
The present invention will be further specified in following embodiment.
Embodiment 1 preparation has the polyvalent alcohol of at least one side carbamateyl
Connect finger-shape condenser, agitator on the bottle at the bottom of the three neck gardens, be connected with the ammonia inlet tube and the thermometer of sintered glass tip.Then this device is placed in the metal vessel that dry ice, water, acetone and sodium-chlor are housed as cryostat, with control reaction temperature.Hydroxyalkyl cyclic carbonate (Glycar packs in this reactor R) and the methyl alcohol of equimolar amount.When the temperature of reactant drops to 15 ℃,, be raised to 32 ℃ up to temperature to wherein feeding ammonia.At this moment reaction stirred and it is as cold as 15 ℃ again.Heavily be covered with and state operation and in infrared spectra, no longer show till the absorption peak of carbonic ether.Depend on the concentration of reaction scale and ammonia.This approximately needs about 12 hours.
At all Glycar RAll be converted to after the carbamate diol, the repacking reactor assembly makes it to carry out the operation of heating, vacuum stripping.Coupling vacuum stripping begins to prevent bumping or system is too expanded in room temperature.Temperature can slowly be raised to 80 ℃, and system vacuum tightness is 28mmHg.When ammonia and methyl alcohol no longer occurring in the gas-chromatography, coupling vacuum stripping is promptly accused and is finished.
Embodiment 2 preparations have the solvent-laden urethane superpolymer of side carbamate-functional
On three neck round-bottomed bottles, load onto prolong, agitator, nitrogen inlet tube and thermometer.Component below in this reactor, packing into:
Component weight
Polyester polyol 2333.60
Methyl propyl ketone 488.54
Neopentyl glycol 70.37
Carbamate diol 141.95
Isophorone diisocyanate (IPDI) 816.75
Methyl ethyl ketone 192.62
4043.83
After all above-mentioned components add, reaction mixture is heated to 210 °F, carry out being raised to about 225 °F owing to exothermic heat of reaction makes temperature in the process in reaction.After the heat release, temperature of charge remain on 225-230 °F three hours, at this moment carry out first time NCO number and measure.Target value is (0.26-0.28) meq NCO/ gram resin.When the NCO number reaches this scope, in the termination procedure of reaction, add 143.15 gram TriMethylolPropane(TMP)s (TMP).After adding TMP, continue reaction 1.5 hours, survey the NCO number at last again one time.Measure when the NCO number and to show that when no longer having NCO, reaction is promptly accused and finished, and at this moment reactant is cooled to 190 °F, adds 813.09 gram Exxate again R800.
Embodiment 3 preparations have the aqueous polyurethane superpolymer of side carbamate-functional
Installing prolong, agitator, nitrogen inlet tube and thermometer on the bottle at the bottom of the three neck gardens.The following component of packing in this reactor
Component weight
Polyester polyol 1180.04
Neopentyl glycol 11.79
Carbamate diol 35.58
Isophorone diisocyanate (IPDI) 413.01
Dimethylol propionic acid 61.41
Methyl ethyl ketone 97.40
2046.28
After all above-mentioned components are all added, reaction mixture is heated to 210 °F.When reaction is carried out, there is exothermic phenomenon to take place slightly, thereby makes temperature be raised to 225 ℃.After the heat release, temperature of reaction maintain 225-230 °F three hours, carry out first time NCO number then and measure.Target value is between 0.29-0.30meq NCO/ gram resin.When the NCO number reaches this scope, add 82.96 gram TriMethylolPropane(TMP)s (TMP), the termination procedure of reacting.Add TMP and keep reaction 1.5 hours later on, survey the NCO number at last again one time.When mensuration shows when not having NCO, reaction is promptly accused and is finished, and can be cooled to 190 °F to reactant, adds 162 gram propyl carbinols.Again reactant is cooled to 180 °F, adds 162.67 gram dimethylethanolamines (DMEA), mix 1 hour to finish the salinization stage of reactant.After the placement, the temperature of reactant drops to 150 ℃, at this moment adds 1667.41 gram deionization (DI) water in container.Add after the deionized water, reactant is mixed two hours to finish the dispersion process of resin.
Embodiment 4 preparations have the solvent-laden urethane superpolymer of side carbamate-functional
On three-necked bottle, install prolong, agitator, nitrogen inlet tube and thermometer.Add following component in this reactor:
Component weight
Polyester polyvalent alcohol 1732.49
Methyl propyl ketone 362.69
Neopentyl glycol 113.14
Carbamate diol 59.11
Isophorone diisocyanate (IPDI) 651.71
Methyl ethyl ketone 143.00
Dibutyl tin two lauric acid salt 0.05
3063.65
After all above-mentioned components have all added in the reactor, reaction mixture is heated to 210 °F.Carry out can be observed in the process in reaction exothermic phenomenon is arranged slightly, thereby make temperature of charge rise to about 225 °F.After the heat release, temperature of charge maintain 225-230 °F three hours, remake for the first time the NCO number and measure.Target value is 0.24-0.25meq NCO/ gram resin.When the NCO number reaches this scope, add 95.95 gram TMP, the termination procedure of reacting.After adding TMP, reactant was kept 1.5 hours, surveyed the NCO number at last again one time.Measure when the NCO number and to show that when not having NCO, reaction is promptly accused and finished.Reactant is cooled to 190 °F, adds 840.39 gram Exxate R800, reaction is promptly finished.
Embodiment 5 preparations have the solvent-laden urethane superpolymer of urea groups with the band side carbamate-functional of enhancement dispersing property.
On three-necked bottle, install prolong, agitator, nitrogen inlet tube and thermometer.The following component of packing in this reactor:
Component weight
Polyester polyvalent alcohol 1732.49
Methyl propyl ketone 362.69
Neopentyl glycol 113.14
Carbamate diol 59.11
Isophorone diisocyanate (IPDI) 651.71
Methyl ethyl ketone 143.00
Dibutyl tin two lauric acid salt 0.05
3063.65
After all above-mentioned components are added, reaction mixture is heated to 210 °F.Can be observed when reaction is carried out has exothermic phenomenon slightly, thereby makes temperature of charge rise to 225 °F.After the heat release, with temperature of charge maintain 225-230 °F three hours, carry out the mensuration of NCO number for the first time then.Target value is (0.26-0.28) meq NCO/ gram resin.When the NCO number reaches this scope, promptly temperature of charge is cooled to 200 steps to prepare to seal end group.In sealing end group step, add 74.95 gram diethanolamine (DEOA) then, and reaction was kept 1 hour.1 advances the back last NCO of mensuration number for a short time.Reaction is not accused and is finished when there has not been NCO in the demonstration of NCO number mensuration.At this moment temperature of charge is cooled to 190 °F, and adds 840.39 gram Exxate R800, subsequently this material cool to room temperature.
Embodiment 6
Under agitation order adds following component and prepares a kind of solvent-laden Clear paint prescription.After all components add and fully stir, coating is filtered in the container in order to using later on.
The component parts by weight
1. have the side carbamate-functional
Urethane resin (embodiment 1) 300.00
2. melamine crosslinker Resimene R747
Annotate: the melamine of other type can basis
Need to replace a kind of 80.00 of selection here
3.Tinuvin R384B UVA photostabilizer 7.50
4.Tinuvin R123 N-alkoxy hindered amines 2.40
5.Nacure RThe acid catalyst 3.60 of 5225 amido protectings
6. Methyl amyl ketone 11.40
7. propyl carbinol 75.00
8.Exxate RThe acetic acid alkyl ester 100.00 of 800 high boiling primary alcohols
Embodiment 7
Prepare a kind of aqueous white priming paint prescription by under agitation being sequentially added into following component.After all components are added into and fully stir, coating is filtered in the container in order to using later on.
The component parts by weight
1. 3% aqueous solution 12.88 of clay rheological agent
2. melamine X-linking agent Resimene RX-747 5.80
3. solvent Dowanol RDPM 1.45
4. band side carbamate-functional
Urethane resin (embodiment 3) 26.43
5. Xun Zheng silica rheological agent 6.84
6. white pigment cream 44.03
7．Tinuvim R1130 0.33
8.Nacure2500, the acid catalyst 1.80 of amido protecting
9. the dimethylethanolamine of regulation system pH value usefulness
20% solution 0.44 in deionized water
100.00
Embodiment 8
By under agitation being sequentially added into the priming paint prescription that following component prepares a kind of solvent-laden white.After all components is added into and fully stirs, promptly coating is filled in the container in order to using later on.
The component parts by weight
1. melamine RX-linking agent Cymel R327 12.00
2. melamine RX-linking agent Cymel R1,158 4.56
3. solvent Exxate R1,000 4.78
4. the microgel rheology control agent 16.45
5. have the side carbamate-functional
Urethane superpolymer (referring to embodiment 4) 10.73
6. flexible high solids content band hydroxyl functional group's acrylic resin 6.32
7. flowing additive Coroc RA-620-A2 0.16
8. solvent xylene 0.15
9．Tinuvin R1130 1.08
10. white pigment cream 37.49
11. n-butyl acetate 4.15
The formulation for coating material of the foregoing description 6-8 is sprayed on the panel that is for experiment, by drying the coating after curing promptly forms hard curing.
By the preferred specific embodiment of reference, the present invention is at large described.But should be understood that in the spirit and scope of the present invention and change and improvement with interior also can making.

Claims (13)

1. method for preparing the urethane with side carbamateyl is characterized in that its adopts the following step:
(a), open the ring of cyclic carbonate and form the polyvalent alcohol that has at least one side carbamateyl by having at least the compound of a cyclic carbonate group and ammonia, ammonium hydroxide or primary amine to react; With
(b) make and contain in steps polyvalent alcohol that (a) make and the mixture of polyisocyanates reacts, have the urethane of side carbamateyl with formation.
2. the method for claim 1 is characterized by, and the urethane that obtains is sealed end group with the end-capping reagent that contains reactive hydrogen.
3. the method for claim 2 is characterized by, and described compound with cyclic carbonate group prepares by hydroxyalkyl cyclic carbonate and polyisocyanates or multi-anhydride are reacted.
4. the method for claim 2 is characterized by, and described compound with cyclic carbonate group is by polyepoxide and CO 2React and prepare.
5. the method for claim 1 is characterized by, and said compound with cyclic carbonate group is a kind of hydroxyalkyl cyclic carbonate.
6. the method for claim 1 is characterized by, and the mixture in the step (b) contains further also that another contains the compound of a plurality of reactive hydrogens at least.
7. the method for claim 6 is characterized by, and the described compound that contains reactive hydrogen is a polyester polyol.
8. the method for claim 5 is characterized by, and the described compound that contains reactive hydrogen is the dibasic alcohol that has carboxyl.
9. the method for claim 1 is characterized by, and the mixture in the step (b) also further contains the pure and mild dibasic alcohol that has carboxyl of polyester polyols.
10. the urethane that each method makes among the claim 1-9 is used to prepare the purposes of curable coating composition.
11. the purposes of claim 10 is characterized by, described curable coating composition contains:
(1) urethane that each method makes among the claim 1-9, and
(2) have a plurality of can with the solidifying agent of the group of carbamate radical reaction.
12. the purposes of claim 11 is characterized by, described solidifying agent is an aminoplastics.
13. the purposes of claim 12 is characterized by, this aminoplastics is melamine resin.
CN95120881A 1994-12-21 1995-12-20 Polyurethane polymer or oligomer having carbamate groups, method for its preparation, and coating composition Expired - Fee Related CN1073579C (en)

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CN1139123A (en) 1997-01-01
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EP0718334A1 (en) 1996-06-26
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US5723552A (en) 1998-03-03
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JP3722891B2 (en) 2005-11-30
MX198476B (en) 2000-09-06
US5827931A (en) 1998-10-27
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US5726274A (en) 1998-03-10
US5659003A (en) 1997-08-19

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